Process of making motor-fuel



C. ELLIS. PROCESS OF MAKING "010R FUEL.

APPLICATIOII min 5.21. ma. uneven nic. I2. ma.

Patented Oct. 7, 1919.

UNITED STATES PATENT OFFICE.

CARLETON ELLIS, OF MONTCLAIR, NEW JERSEY, ASSIGNOR TO ELLIS-FOSTER COMPANY, A CORPORATION OF NEW JERSEY.

PROCESS OF MAKING MOTOR-FUEL.

Specification of Letters Patent.

Patented Oct. 7, 1919.

Application filed August 21, lglt, Serial No. 785,855. Renewed December 12, 1918. Serial No. 266,512.

To all whom it ma concern:

Be it known t at I, CARLETON ELLIS, a citizen of the United States, and a resident of Montclair, in the county of Essex and State of New Jersey, have invented certain new and useful Improvements in Processes of Making Motor-Fuel, of which the following is a specification.

his invention relates to a process of making or making and treatin a gasolene-like material to produce a pro not suitable for use in automobile engines and the like, and relates in particular to the treatment of gasolene-like material obtained through pyrogenetic decomposition of kerosene or heavier oils such, for example, as may be obtained by passing kerosene through heated tubes and the like.

In carryingout my process I may start with a petroleum oil say kerosene which may have a gravity of 42 B. or thereabout. This may be passed through a heated conduit, as for example, an iron pipe of a len h preferably 50-100 feet which pipe is pre erably heated to around 425 or 480 C. and in some-cases may be packed loosely with suitable contacting material such as nickel plated fragments of iron of irregular shape. Also in some cases water may be introduced with the kerosene or other oil, if desired, al though tending to somewhat retard the splitting operation, but on the other hand, sometimes having a favorable influence on the character of the resulting product. Five per cent. of water calculated on the amount of oil introduced, is usually a satisfactory proportion. As stated, the use of water is optional.

The product emanating from the conduit forming the heating zone consists of fractions which on the one hand are lighter than the kerosene or the oil employed and on the other hand contain heavier products due to polymerization during the treatment. Very curiously these are oftentimes so proportioned that the specific gravity of the light oil counter-balances that of the heavier oil formed and the mixed distillate may thus show approximately the same specific gravity as the original kerosene or similar oil. For instance, a 42 gravity kerosene may give a product of precisely this gravity or perhaps 42.5 or 43 Be. which may contain or so of gasolene-like material.

The product obtained by this pyrogenetic treatment is separated into lighter and heavier parts by fractional condensation which may be followed if desired by fractional distillation and a gasolene fraction boiling to 125 (J. or 150 C. obtained. This fraction is usually of brown color and of disagreeable odor.

When one attempts to refine it in the ordinary way using concentrated sulfuric acid followed by alkali, the gasolene tends to blacken or darken through formation of a large amount of tar and coke-like material and this discolorization is not easily removed by water and alkali. In oil refining operations, so objectionable is the diluting effect of any water which may be present in the oil on the strong acid used that it has been recommended, for example, to very carefully dry the oil prior to the actual acid refining step. With cracked raw material of the present process this is not desirable, unless, of course, excessive amounts of water be accidentally present. I have found that acid which is more or less diluted with water acts more satisfactorily than the concentrated acid, which is contrary to ex ectations. Acid of 40-70% strength of s11 furic anhydrid causes a better and more satisfactor conversion of the unsaturated material.

Kn illustrative example will serve to make this clear. Kerosene of 42 B. was run through a tube of suitable length heated to such a temperature that the escaping oil vapors were maintained at a temperature about 465 C. which required a temperature about the tube of approximatel 630 C. The vapors were passed throng an air condenser then through a water condenser and finally the gases escaping from the latter were bubbled through heavy oil in order to remove some of the entrained condensable material. A portion of the condensate was distilled and cut at 105 C. and a fraction of gasolenelike material hawing a gravity of B. was obtained which amounted to 25% of the total condensate taken for distillation. When the same condensate was cut at 140 C. instead of 105 C. the fraction obtained amounted to 27% and had a gravity of 545 B. Similarly when a third portion of the condensate was cut at 150 C. a fraction amounting to 32% of the original condensate was obtained and the gravity of this mate rial was 53 Be. The residue in the retort had a gravity of approximately 38 B6,

From the heavy washing oil through which the gases from the cracking stage were bubbled as described above a further yield of gasolene-like material was obtained.

. The gravity of the product as drawn from the heated tube was 43 1315., or only one degree lighter than the original kerosene. On exposing the fraction distilling over below 100 C. to air in an open dish, the major proportion of the material evaporated leav ing a thick greasy material of whitish color resembling very soft vaseline. On very careful distillation of the crude gasolene, or on passing air through the latter a similar product was formed which separated to, some extent from the volatile hydrocarbons.

The thick greasy material referred to above, which may for convenience be called polymer A, and which probably was a product of polymerization and oxidation, decomposed when heated, vapor being given off at 110 C. and a mild explosion taking placaat 125 C. This applies to the separated polymer A as in solution in the hydrocarbon the heating may be carried up'to 160 C. or so without explosion, but usually with the disengagement of some gas. \Vhen the material is heated to 125 C., the reaction which takes place causes the formation of considerable gas and the production of a brownish liquid of somewhat thinner consistency than polymer A. The brown liquid may be termed polymer B. This has a tendency to thicken and become quite gummy orfairly solid on exposure to air. The iodin number of polymer A, secured under these circumstances, Was 35.6, while that oipolymer B was 61.3.

A quantity of the crude spirit distilling up to 150 in an ordinary distilling apparatus was fractionated with a rectifying column and the following fractions were obtained:

. Percentage Iodin Fractmns' by volume. number.

Per cent.

No. 1, u to C 9 310 No.2, 7 85 C 8. 4 233 No. 3, 85-100" 0 s. B 218 No. 4,1oo-115 0.. 9. 2 168 No. 5, 115-130" 0.. s 136 No. 6, 130-150 0.. 14 87.8 No. 7, above 150 C 19 53 The color of the different fractions above tabulated varied from practically colorless in Number 1, nearly colorless in Numbers 2 and 3, slightly darker in Numbers 3 and 4, profgressively to rather dark brown products in ractions 6 and 7. All the fractions ignited easily in an open dish at room temperature except fraction 7 which ignited but not as readily. When these fractions are burned in open dishes at resinous-like residue forms in some of them, the largest amount being present in fractions 2 and 3,

genation, but with great difliculty by distillation.

The formation of these resinous or sticky materials in the carbureters of an internal combustion engine ofcourse soon causes trouble. Polymer A may be converted into sulfonated or other products some of which appear to be high polymers by treatment with aqueous sulfuric or hydrochloric acid. When a itated with about 5% of sulfuric acid of 5 strength, the acid quickly turns a deep brown, but the hydrocarbon remains clear, or at the most is only tinted a yellow color. After agitation in this manner, the acid is removed by washing with water and, for example, about 5% of caustic soda solution of 20 B is introduced and the hydrocarbon agitated for a time until reaction is complete; then the product is washed thorouihly with water to remove the alkali.

quantity of this material passed through a carbureter which previously has been weighed was found to leave the carbureter free from resinous traces and any residue, if present, was negligible in amount.

The foregoing illustrates the results obtained with one sample of oil under certain conditions and, of course, considerable variations arise with changes in temperature, pressure and nature of the raw materials.

The above mentioned residue having a gravity of 38 B. when passed through a heated tube under approximately the same conditions, gave a yield of gasolene-like material of which 26% or thereabout was obtained by distilling up to 150 C. This is somewhat less than the percentage of gasolene-like material obtained from the first running using the original kerosene of 42 B. in which case over 30% of gasolene-like material distillingup to 150 C. was secured.

By the term gasolene-like material I do not wish it to be inferred that the product derived in this manner is like gasolene chemically, because ordinary or natural gasolene is either entirely saturated or shows a very slight iodin absorption. The iodin number of the raw or crude gasolene-like material obtained by this method before treatment with sulfuric acid may in some cases range around 100 to 150 and for certain. fractions these may run much higher as indicated above.

Instead of using sulfuric acid under con ditions to produce strict sulfonation and tar formation which takes place when the acid is highly concentrated, I preferably in accordance with the present invention use an acid which has been diluted with water or other dilutin medium so that the strength is lowere as for example to 40-60% or 70% as previousl noted although this percentage may be hig er or lower depending on the iodin number of the oil as well as on its other characteristics and the foregoing is merely set forth in an illustrative sense and I do not wish to be limited to any disclosure of precise procedure as laid down herein, but wish to embrace such equivalent methods of treatment or range of treatment as fall within the scope hereof.

After treating the crude product with sulfuric acid of say 50% strength, a stronger acid may follow as the more readily charred bodies ma be removed by the more dilute acid and urther extraction and refining by stronger acid as 60, 70 or 80% strength may then be brought about. Oxidising agents such as a somewhat dilute solution of chromic acid may be used to improve the color. Filtration or other suitable contact with charcoal also is useful.

The strength of. the sulfuric acid to be employed in carrying out the invention in its preferred aspects may be conveniently found in a practical manner by treating a series of samples of the spirit obtained from the cracking step with acid of different stren ths ranging from about 40% and upward. f a determination of the iodin number is first made to indicate the degree of unsaturation,

' the effect of sulfuric acid may be ascertained in one of two ways. Either the start may be made with strong concentrated acid and then progressively diluted acid used until the correct reaction strength is found. Or 40% acid may be used at the start and acid of progressively increasing strength employed until the correct reaction strength is found by this rocedure. With cracked material of an io in number of between 200 and 300 the latter method is best as the more dilute acid is likely to prove the correct reagent for permanent use. With iodinnumbers below 100 the former method is recommended. If the strength of the acid is too great for desirable practical operation, especially with the products of high iodin numbers, charring or vigorous carbonization will occur and in such cases the cracked material collecting above the sulfuric acid layer after such treatment is usually discolored to such an extent as to be unsatisfactory in appearance as a commercial article while in the acid layer are frequently found carbonized masses. The acid is of a very dark or black color in most cases of this character.

With the preferred or correct strength of acid as found in this manner the reaction mass (acid) is not greatly discolored and carbonized masses are not in evidence. The upper layer of hydrocarbon is of light color and any coloration present is fairly well'removed b treatment with alkali and washing. W en an acid of substantially non-. carbonizing or non-charring strength has .quired over long periods.

thus been ascertained, such strength of acid may be regularly used in large scale operation without further examination if the plant is operated under approximately the same conditions, over an indefinite period. Of course slight variations from day to day in the cracked product do not re ulre rea justment of conditions. Once t e proper strength of acid is found for the manner of operation in hand no change is usually re A slightly larger or smaller proportion of olefines or other unsaturated bodies in the crude cracked spirit does not necessarily call for modification of the strength of the acid as some latitude in this respect is feasible. A light colored or water-white asolene is prepared with diflic-ulty from crac ed oil running high in readily oxidizable olefines! if too concentrated an acid is employed as some coloring matter forms which is soluble in the gasolene and which is not readily extracted by alkali and which can be removed by bleaching agents only at considerable expense. Conse quently to prepare a clear water-white gasolene free from such discolorin agents, the strength of the acid may be a justed as indicated in the foregoing so that carbonizetion will be so slightas not to bring about the objectionable formation of gasolene soluble dyestulfs and the adjustment of the acid to this strength for any given grade of cracked material may be made with small samples first until the desired strength of the acid is found for the particular grade of cracked material under treatment.

Ordinary natural gasolene, as stated, has a low iodin absorption or none at all while the present product has it will be noted, normally, a relatively high iodin number. In spite of this, the aforesaid treatment renders the product relatively stable. Moreover generally speaking it is more volatile than ordinary gasolene. In fact the new product having in one instance a gravity of say 52 B. apparently operates in carbureters equally well as or better than common gasolene of about 54 or 55 Be; The un' saturated condition of the new product apparently renders it more reactive with oxygen enabling greater ease of ignition and more uniform explosion in internal com-- bustion engines.

At a gravity of say 54 B. for both common gasolene and the preferred product of the present invention, the latter in its preferred form shows greater volatility, diffuses more easily, has a lower flash point and is ignited with greater-ease and seemingly is burned more effectively than the former. It appears that a considerable degree of unsaturation is not undesirable if the gasolene has been extracted by acid of predetermined strength as above indicated, as smooth engine operation may be maintained by the use of products of this character. The olefines, etc. which may remain after such extraction, although stable enough to be relatively permanent in storage, are yet apparently sufficiently sensitive to aid in the responsiveness of the fuel when used in internal combustion engines.

My product in its preferred aspects has an iodin number not less than 30, but preferably is higher and even may be in excess of 75 or 100, under some circumstances, and in its preferred form is substantially free from olefines readily forming resinous bodies on exposure to airs In the accompanying drawing a cracking retort is shown with the setting in vertical section and the various condensers, conduits, stills, storage tanks, and acid treating tanks shown in vertical elevation. These drawings depict the apparatus in diagrammatic fashion for illustrative purposes.

In the drawing 1 is the setting of the cracking apparatus or retort. 2 is an inlet for oil and 3 is an inlet for water, when this is used. 4 is a coil of pipes suspended over the grate 5. 6 is an air condenser and 7 a water condenser, the outlet of the latter connects with a trap which in turn leads to the storage tank 9. 10 is a vent pipe for the gases and communicates with the as scrubbing tower 11. 12 is an inlet pipe or the introduction of the scrubbing oil. 13 is a vent pipe for the removal of the unabsorbed gases. 14 is a storage tank for the material coming from the gas scrubbing tower having an outlet pipe 15 leading to the still 17. 16 is a pipe connecting the storage tank 9 with the still 17. 18 is acondenser, 19 a pump, and 20 is a pipe leading from the pump to the acid tank 21. A discharge pipe 22 leads from the latter to the second acid tank 23. A pipe line 24 leads from the tank 23 fee third acid tank 25. 26 is a draw-0E for the finished gasolene material. 27, 28 and 29 which communicate with 30 are draw-ofl's for the removal of the sulfated material from the action of the'sulfuric acid o'n the olefines of the cracked gasolene.

In the operation of this process kerosene or other suitable oil is forced into the coil 4 in which there may be a catalytic material such as fragments of nickel supported on iron, which catalytic material is not here shown. The oily material is heated in the coil to the requisite cracking temperature whereby gasolene and gases and other products are formed and this product is passed through the air condenser and water condenser and a condensate obtained which is collected at the storage tank 9. The gases together with more or less entrained condensable material are passed into the scrub bingtower 11 and are scrubbed, the prod not being collected at the storage tank 14. The material in the tanks 9 and 14 is suitably distilled in the still 17 and the condensed products of a gasolene-like character are passed into the acid tank 21 where they are treated with sulfuric acid of a strength suited to the particular olefine material that is being extracted. In this tank for example, a strength of 4060% acid may be used. The tank is fitted with an agitator which violently mixes the acid and gasolene material so that satisfactory contact with the olefines is obtained. The strength of the acid is of course preferably adjusted so that no undue charring or carbonization occurs. The gasolene material, if not sufliciently treated at this point is run into the tank 23 where it is treated with stronger acid, as for example, beween 60 and strength and if such treatment is not adequate to extract a sufficient amount of the olefine material the product is run into the tank 25 and treated with acid of higher strength, as for example, between 70 and 80% strength of sulfuric anhydrid. The refined gasolene is removed at the outlet 26 and may be washed with alkali in the usual manner. The various extracts of the olefine material in combination with the sulfuric acid are removed by the pipe 30.

The foregoing description is given in detail but it is to be understood that such illustrative matter is not to be construed as a. limitation defining the invention in any narrower sense than is comprehended by the substance of the appended claims.

To recapitulate, my process comprises the production of lighter from heavier hydrocarbons to make a product adapted for use as motor spirit, which comprises exposing the heavier hydrocarbon material to a cracking temperature as for example by passage of said material through a heated zone to effect decomposition, and in subjecting the products of such decomposition, particularly the lighter fractions, to the action of an acid comprising sulfuric acid of predetermined strength; whereby easily oxidizable olefines are extracted and in adjusting the strength of the acid to suitably extract these and other olefine bodies which are to be removed, employing further extraction with stronger acid if required to remove olefines not extracted by the weaker acid; and my invention also embraces, as a preferred product of said process, a motor spirit consisting of or comprising cracked gasolene material, that is gasolene material made by heat decomposition of a heavier oil referably substantially freed from ole e or kindred bodies of an easilyoxidizable or resin-forming character vet containing some unsaturated bodies, and in the preferred form exhibiting an iodin absorption value or number of 30 or over, while ordinarily having a flash point lower than normal natural gasolene of corresponding specific gravity.

The product of the herein described process is claimed in my copending divisional application, Serial No. 196,204, filed October 12 1917.

What I claim is 1. A process of producing gasolene-like material adapted for use as a motor fuel comprising subjecting a heavier hydrocarbon to a cracking temperature whereby such hidrocarbon is cracked, separating gasolene- 1i e material from the resulting product and subjecting such asolene-like material to the action of dilute sulfuric acid.

2. A process of producing gasolene-like material adapted for use as a motor fuel comprising subjecting a heavier hydrocarbon to a cracking temperature whereby such hydrocarbon is cracked and gasolene-like material containing a substantial amount of unsaturated bodies produced, separating gasolene-like material containing a substantial amount of unsaturated bodies from the resulting product and subjecting the .separated material to the action of sulfuric acid of such strength that in its reaction with the unsaturated bodies present in the asolene-like material a portion of such odies are removed and nosubstantial and permanent discoloration of the gasolene-like material is produced.

3. A process of producing gasolene-like material adapted for use as a motor fuel comprising subjecting a heavier hydrocarbon to a cracking temperature whereby such hydrocarbon is cracked, and gasolene-like material containing a substantial amount of unsaturated bodies produced, separating gasolene-like material containing a substantial amount of unsaturated bodies from the resulting product and subjecting the separated material to the action of diluted sulfuric acid of a strength to remove the undesirable more readily oxidizable unsaturated bodies without removing all of such unsaturated bodies.

4. A process of producing gasolene-like material adapted for use as a motor fuel comprising passing a heavierhydrocarbon through a heated zone whereby such hydrocarbon is cracked, separating gasolene'like material from the resulting product and subjecting such asolene-like material to the action of dilute sulfuric acid.

5. A process comprising treating cracked gasolene-like material containing unsaturated bodies with diluted sulfuricacid.

6. A process comprising treating gasolene-like material [containing a substantial amount of unsaturated bodies with diluted sulfuric acid of such strength that no substantial carbonization occurs.

7. A process comprising treating cracked gasolene-like materials containing unsaturated bodies with diluted sulfuric acid, the strength of the acid being proportioned with respect to the content of unsaturated bodies to remove a part and leave a part of such unsaturated bodies.

8. A process comprising treating cracked gasolene-like material having an iodin number of not less than 30 with diluted sulfuric acid whereby the iodin number is lessened but the product left with a substantial amount of unsaturated bodies.

9. A process of treating hydrocarbons comprising subjeicting a hydrocanbon oil heavier than asolene to a cracking temperature where y a mixture of saturated and unsaturated hydrocarbons is obtained, and subjecting a portion of the products of the cracking operation consisting of saturated and unsaturated hydrocarbons, to the action of diluted sulfuric acid of such strength that initially light colored acid turns to a, deep brown color upon being added to the mixture of saturated and unsaturated hydrocarbons.

10. A process of treating hydrocarbons comprisin subjecting a mixture of saturated an unsaturated hydrocarbons obtained by cracking a hydrocarbon-oil to suecessive treatment with diluted sulfuric acid whereby a substantial portion but not all of the unsaturated hydrocarbons are removed.

11. A process of treating hydrocarbons comprising subjecting a mixture of saturated and unsaturated hydrocarbons obtained by cracking a hydrocarbon oil to successive treatments with diluted sulfuric acid of different strengths, the strenfih of the acid employed in each treatment, ing such that initially light colored acid is colored a deep brown but no undue carbonization occurs upon being added to the mixture of saturated and unsaturated hydrocarbons.

Signed at Montclair, in the county -of Essex and State of New Jersey, this 15th day of August A. D. 1913.

- CARLETON ELLIS. Witnesses:

B. M. Ems NATHANIEL Fos'ran.

oloLAlms'.

1,318 061.0m-kton Ellie, Monbclair, N. J. Pnoczaa or Mumm Mum: iatent dated October 7, 1919.. Disclaimer filed May 12, 1927, by the aaslg'nec by mesne ,assignments, Strmdard Dovelopmmt Company Hereby enters this disclaimer to that modification of the rocess set forth in lines 86-8 of page 4 wherein the gasoline is treated with acid tween 70 and 85% of sulphuric anhydrid and disclaims from the scope of all the claims any process wherein acid employed is not diluted below the strength of ordinary oil of vitriol, 1'. 93% H,SO

[OfioiaZ Gazette, Mag .24, 1.927.] 

